AU682624B2

AU682624B2 - New sunscreen agents, photoprotective cosmetic compositions containing them and uses

Info

Publication number: AU682624B2
Application number: AU31700/95A
Authority: AU
Inventors: Alain Lagrange; Madeleine Leduc; Herve Richard
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1994-10-07
Filing date: 1995-09-18
Publication date: 1997-10-09
Anticipated expiration: 2015-09-18
Also published as: ES2112029T3; DE69501033D1; DE69501033T2; HUT73748A; EP0708108B1; BR9504792A; KR960014137A; PL310850A1; US5962484A; FR2725448B1; CA2160073C; AU3170095A; JPH08188581A; CA2160073A1; HU9502926D0; FR2725448A1; JP2885669B2; US5663270A; CN1126725A; KR0171686B1

Abstract

Benzotriazolylphenol siloxane or silane cpds. of formula (I)-(III) are new, where R = 1-10C alkyl, phenyl and/or CH2CH2F3, at least 80% being Me; B = R or A; R' = 1-8C alkyl and/or phenyl; r = 0-50; s = 0-20; provided that at least one B is A when s = O; u = 1-6; t = 0-10; provided that t+u = 3 or more; A = a gp. of formula (IV), where Y = 1-8C alkyl, halogen and/or 1-4C alkoxy, or adjacent X+Y = 1-2C alkylenedioxy; X = O or NH; Z = H or 1-4C alkyl; n = 0-3; m = 0 or 1, provided that n = 1-3 and at least one Y is alkoxy when m = 0 or when m = 1 and X = NH; p = 1-10. Also claimed are intermediates of formula (IVa).

Description

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Applicant:

L'OREAL

e eq..

C. SW C C

C

C.

C C

C

S C C. C 4C *5 C *5*C

C

CC

Invention Title: NEW SUNSCREEN AGENTS, PHOTOPROTECTIVE COSMETIC COMPOSITIONS CONTAINING THEM AND USES The following statement is a full description of this inventior,, including the best method of performing it known to me/us: NEW SUNSCREEN AGENTS, PHOTOPROTECTIVE COSMETIC COMPOSITIONS CONTAINING THEM AND USES The present invention relates to new compounds of the short-chain, linear or cyclic diorganosiloxane type or of the triorganosilane type, possessing the common feature of all having at least one alkoxybenzotriazole function, these compounds being usable more especially as organic sunscreen agents in cosmetic compositions intended for protecting the skin and hair against ultraviolet radiation. The invention also relates to the use of the said compounds in the abovementioned cosmetic application, as well as to cosmetic compositions having improved properties containing them. Lastly, it also relates, as new industrial products which are useful per se, in particular as screening agents for photoprotective cosmetic compositions for the skin and hair, to the ethylenically unsaturated alkoxybenzotriazoles used in the synthesis of the new compounds mentioned above.

20 It is known that light radiation of wavelengths between 280 nm and 400 nm permits tanning S* of the human epidermis, and that rays of wavelengths between, more especially, 280 and 320 nm, known by the name of UV-B, cause erythema and skin burns which can 25 impair the development of the natural tan; this UV-B radiation should hence be screened out.

It is also known that UV-A rays, of wavelengths between 320 and 400 nm, which cause tanning

LIC~I

2 of the skin, are liable to induce adverse changes in the latter, in particular in the case of sensitive skin or skin constantly exposed to solar radiation. UV-A rays cause, in particular, a loss of elasticity of the skin and the appearance of wrinkles leading to premature skin ageing. They promote triggering of the erythematous reaction or enhance this reaction in some subjects, and can even be the source of phototoxic or photoallergic reactions. It is hence desirable to screen out UV-A radiation also.

Many compounds intended for photoprotection (UV-A and/or UTV-B) of the skin have been proposed to date.

Most of them are aromatic compounds displaying an absorption of UV rays in the region between 280 and 315 nm or in the region between 315 and 400 nm, or else in both of these regions together. They are, more often than not, formulated in antisun compositions which take the form of an oil-in-water 20 type emulsion (that is to say a cosmetically acceptable vehicle consisting of an aqueous continuous dispersing phase and an oily discontinuous disperse phase) and which hence contain, at various concentrations, one or more traditional lipophilic and/or hydrophilic organic 25 screening agents containing an aromatic function, capable of selectively absorbing harmful UV radiation, these screening agents (and the amounts thereof) being selected in accordance with the desired specific I protection factor (the specific protection factor (SPF) being expressed mathematically by the ratio of the irradiation time needed to reach the erythemogenic threshold with the UV screening agent to the time needed to reach the erythemogenic threshold without a UV screening agent).

Apart from their screening power, these compounds having anti-UV activity must also display good cosmetic properties in the compositions in which they are contained, good solubility in common solvents, and especially fats such as oils and greases, and also good resistance to water and to perspiration (durable effect).

Among all the aromatic compounds which have been recommended for this purpose, p-aminobenzoic acid derivatives, benzylidenecamphor derivatives, cinnamic acid derivatives and benzotriazole derivatives may be 9 ~mentioned in particular. However, some of these substances do not display all the properties required 20 for an acceptable use as UV screening agents in antisun compositions. In particular, their intrinsic screening power may be insufficient, their solubility in the different types of formulations used in relation to sun protection is not always sufficiently good (fat 25 solubility in particular), they may not possess sufficient stability to light (photostability) and they

S*

may also display poor resistance to water and to sweat.

It is also desirable for these screening substances not I l-r a Ir~ew 4 to penetrate the skin.

Thus, in the particular case of screening substances of the benzotriazole type, it has been sought to obtain products which have improved properties, especially in respect of their fat solubility and their cosmetic character, by effecting attachment of the benzotriazole screening group by grafting (hydrosilylation) onto a macromolecular chain of the silicone (organopolysiloxane) type. This technique, described in Patent Application EP 0,392,883 in the name of the Applicant, does indeed lead to advantageous compounds (these products are known by the general name of "silicone screening agents"), but the fat-soluble character of the latter can still appear to be inadequate and, furthermore, in order to obtain satisfactory screening properties with this type of product, it is often necessary to employ relatively 0 large amounts of these screening polymers, resulting in poor cosmetic properties in respect of the formulations 20 in which they are contained.

00 The present invention is directed towards S. solving the above problems, by providing new compounds of the silicone screening agent type containing a benzotriazole function, which display improved *0 0 25 properties, in particular in respect of their solubility in fats, their cosmetic properties and their intrinsic absorbing power with respect to the UV.

Still more specifically, it was found -L ~L1I= according to the present invention that, by combining, in particular by a hydrosilylation reaction, one or more particular benzotriazole derivatives, namely, more specifically, alkoxybenzotriazoles, with a particular linear or cyclic silicone chain or a particular silane, it was possible to arrive at new compounds of the silicone screening agent type overcoming the drawbacks of the silicone screening agents of the prior art, these new compounds displaying in particular very high screening properties, very good solubility in common organic solvents, and in particular fats such as oils, and also excellent cosmetic properties, making them especially suitable for use as sunscreen agents in, or for the preparation of, cosmetic compositions intended for protecting the skin and/or hair against ultraviolet radiation.

Thus, the first subject of the present invention is new compounds which are characterized in that they correspond to one of the following formulae 20 to R R R R B: B0_ 0 ii-O-- Si- B (1) RR r L e o _r R R si- i-o I (2 t

U

A-Si(R') 3 (3) in which formulae to R, which may be identical or different, are chosen from C 1 alkyl, phenyl and 3,3,3-trifluoropropyl radicals, at least 80 in numerical terms of the radicals R being methyl, B, which may be identical or different, are chosen from the above radicals R and the radical A defined below, which may be identical or different, 10 are chosen from C 1 alkyl radicals and phenyl S" radicals, r is an integer between 0 and 50 inclusive, and s is an integer between 0 and 20 inclusive, on condition that, if s is zero, then at least one of the 15 two symbols B denotes A, u is an integer between 1 and 6 inclusive, S....and t is an integer between 0 and 10 inclusive, on the' understanding that t u is equal to or greater than 3, I I 7 and the symbol A denotes a univalent radical linked directly to a silicon atom, and which corresponds to the following formula N OH

I

N Y(y)n 4

(CH

2 p-CH-CH 2

Z

in which formula Y, which may be identical or different, are chosen from CI-C alkyl radicals, halogens and C 1

-C

4 alkoxy radicals, on the understanding that, in the latter case, two adjacent radicals Y on the same aromatic ring can form together an alkylidenedioxy group in which the alkylidene group contains from 1 to coo 2 carbon atoms, X represents 0 or NH, Z represents hydrogen or a Cl-C 4 alkyl radical, 15 n is an integer between 0 and 3 inclusive, m is 0 or 1, on the understanding that, when m is zero, or when m is equal to 1 and X repreEsents NH, then necessarily n cannot be zero and (ii) at least one of the radicals Y is an alkoxy radical, p represents an integer between 1 and L- 8 inclusive.

In the above formulae to A hence represents the group derived from benzotriazole which, after attachment to the starting short silicone chain or to the starting silane, endows the compounds of the linear diorganosiloxane type (formula or cyclic diorganosiloxane type (formula or of the triorganosilane type (formula with absorbing properties with respect to ultraviolet in a wavelength region which can range from 280 to 400 nm. As menr io:'ed before, and as is apparent from the definition oi the., formula given above, this group necessarily possesses at least one alkoxy function attached to at least one of the two aromatic rings of the benzotriazole, it being possible for this alkoxy function to be supplied either by a substituent Y or by the chain link which provides the coupling of the benzotriazole to the silicone chain or to the silane.

One of the great advantages of the compounds according 20 to the invention is that, depending on the position occupied by this/these alkoxy group(s) on the screening unit A, it is possible to obtain screening agents which are either purely UV-A or, on the contrary, purely UV-B, with extinction coefficients in all cases well 25 above those obtained with the silicone screening agents of the prior art. Thus, purely by way of example, derivatives possessing an alkoxy group at the ortho iti ith respect to the hydroxyl group orne by position with respect to the hydroxyl group borne by 9 the benzene ring (position 3) give silicone screening agents predominantly absorbing in the UV-B, whereas derivatives possessing an alkoxy group at the meta position positions 4 and/or 6) with respect to this same hydroxyl group give silicone screening agents predoniinantly absorbing in the UV-A.

As is apparent from the formula given above, the coupling of the chain link (CH2)p-CH(Z)-CH 2 to the benzotriazole unit, which hence provides for connection of the said benzotriazole unit to the silicon atom of the silicone chain or of the silane, can, according to the present invention, take place in all the available positions afforded by the two aromatic rings of the benzotriazole: 6' N OH 2 15 Preferably, this coupling takes place at position 3, 4 5 (aromatic ring bearing the hydroxyl function) or 4' (benzene ring adjoining the triazole ring), and still more preferably at position 3, 4 or Likewise, the coupling of the substituent 20 unit Y can take place in all the other available positions within the benzotriazole. However, this coupling preferably takes place at position 3, 4, and/or 6.

~sraa sr R IS~~gi~ ~R In the above formulae to the alkyl radicals can be linear or branched and chosen, in particular, from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-amyl, isoamyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl and tert-octyl radicals. Preferred alkyl radicals R, R' and B according to the invention are methyl, ethyl, propyl, n-butyl, n-octyl and 2-ethylhexyl radicals. Still more preferably, the radicals R, R' and B are all methyl radicals.

Among the compounds of formulae to (3) above, it is preferable to employ those corresponding to the formula or to the formula that is to say short-chain, linear or cyclic diorganosiloxanes.

Among linear or cyclic diorganosiloxanes falling within the scope of the present invention, statistical or well-defined block-containing tot derivatives displaying at least one, and still more *4 preferably all, of the following features are preferred 20 more especially: R is alkyl and is still more preferably methyl, B is alkyl and still more preferably methyl (this applies to the linear compounds of formula 25 r is between 0 and 3 inclusive; s is between 0 and 3 inclusive (this applies to the linear o compounds of formula t+u is between 3 and 5 (this applies to the I 11 cyclic compounds of formula n is not zero and is preferably equal to 1 or 2, and Y is then chosen from methyl, tert-butyl and

C

1

-C

4 alkoxy, but preferably from C 1

-C

4 alkoxy, and is still more preferably methoxy, Z is hydrogen or methyl, X represents O (m d 0), p is equal to 1, on the understanding that, in all cases, at least one alkoxy function is coupled directly to the benzotriazole derivative.

To prepare the silicone screening agents of formulae and it is possible to proceed in a traditional manner, employing a hydrosilylation reaction (namely =Si-H CH 2 Si-CH 2

-CH-)

starting from the corresponding silicone in which, for example, all the radicals A are hydrogen atoms. This starting silicone is designated hereinafter 20 SiH-containing derivative; the SiH groups may be present in the silicone chain and/or at the ends of the silicone chain. These SiH-containing derivatives are 5o well-known products in the silicone industry, and are o* generally available on the market. They are, for example, described in American Patents US-A-3,220,972, SUS-A-3,697,473 and US-A-4,340,709.

This SiH-containing derivative may hence be represented either by the following formula (la): dF 4 B' si- o si-- (la) R R B

B'

r s in which R, r and s have the meaning given above for the formula and the radicals which may be identical or different, are chosen from the radicals R and a hydrogen atom, or by the following formula (2a): 1R -s-o o- I (2a) R

H

t U oe1 in which R, t and u have the meaning given above for the formula S* On this SiH-containing derivative of formulae (la) or a traditional hydrosilylation reaction, 10 carried out in the presence of a catalytically *efiective amount of a platinum-based catalyst, is hence performed on an organic benotriazole derivative of the following formula (4a): 13 N OH N (y) n (4a) (X)m-(CH 2 )p-C=CH 2

Z

in which Y, X, Z, n, m and p have the meaning given above for the formula Processes suitable for the preparation of the products of formula (4a) above are described, in particular, in Patents US-4,316,033 and US-4,328,346.

In addition, the details of the working conditions to be followed for conducting the hydrosilylation reaction between the compounds of formula (la) or (2a) above with the uompound of formula 10 (4a) above are given in Patent Application EP-0,392,883 cited above, the teaching of which is, in this respect, completely included in the present description by way of reference.

As regards the preparation of the screening 15 agents of the triorganosilane type of formula given earlier, it is possible to proceed as described above, still by a hydrosilylation reaction, between a starting silane of formula 3 Si-H (formula in which R' has the same meaning as for the compound of formula and an organic benzotriazole derivative of formula (4a) defined hereinbefore.

As mentioned earlier, the monoethylenically

I

14 unsaturated organic benzotriazole derivatives of formula (4a) above constitute new products which are useful per se and, on this basis, also form an integral part of the present invention, as does their use as sunscreen agents in the UV-A and/or UV-B range, especially in cosmetic compositions intended for photoprotection of the skin or hair.

Relative to the silicone screening agents of the prior art as are described in Patent Application EP 0,392,883, the silicone screening agents according to the invention hence display one or several essential structural differences which are the source of their exceptional properties: the silicone chains onto which the benzotriazole unit is grafted are, in the first place, much shorter; next, the unit derived from benzotriazole always bears at least one alkoxy function.

As mentioned earlier, the compounds of S• formulae to above display excellent intrinsic screening power with respect to ultraviolet radiation S(UV-A or UV-B, depending on the structure of the product). By mixing products of different structure, that is to say, more specifically, by mixing products according to the invention displaying purely UV-A activity with products according to the invention displaying purely UV-B activity, it is thus possible to have at one's disposal a composition which will display overall an exceptional screening activity over the entire range of harmful UV (UV-A UV-B), which constitutes a considerable advantage. In addition, by virtue of their strongly fat-soluble character, the compounds of formulae to above may be used at high concentrations, thereby endowing the final compositions with very high specific protection factors; moreover, they distribute themselves uniformly in the traditional cosmetic vehicles containing at least one fatty phase or a cosmetically acceptable organic solvent, and may thus be applied to the skin or hair in order to form an effective protective film.

Lastly, their cosmetic properties are very good, namely, in particular, these products, relative to the silicone screening agents of the prior art, less sticky and make the skin or hair softer.

Hence the subject of the present invention is also a cosmetic composition comprising, in a *cosmetically acceptable vehicle preferably containing at least one fatty phase or one organic solvent, an effective amount of at least one compound of formulae to defined above.

The compounds of formulae to are generally present in proportions of between 0.1 and .20 by weight, and preferably between 0.5 and 10 by weight, relative to the total weight of the t :composition.

The cosmetic composition of the invention may be used as a protective cmposition for the human LY -II 16 epidermis or hair against ultraviolet rays, as an antisun composition or as a make-up product.- This composition may take the form, in particular, of a lotion, thickened lotion, gel, cream, milk, powder or solid stick, and be packaged, where appropriate, as an aerosol and take the form of a mousse or spray.

It can contain the cosmetic adjuvants customarily used in the field, such as fats, organic solvents, silicones, thickeners, emollients, additional sunscreen agents, foam inhibitors, hydrating agents, perfumes, preservatives, surfactants, fillers, sequestering agents, anionic, cationic, nonionic or amphoteric polymers or mixtures thereof, propellants, alkalinizing or acidifying agents, colorants, pigments or nanopigments, especially those designed to provide for an additional photoprotective effect by physically *blocking the ultraviolet radiation, or any other ingredient customarily used in cosmetics, especially for the manufacture of antisun compositions.

Among organic solvents, lower polyols and alcohols, such as ethanol, isopropanol, propylene glycol, glycerol and sorbitol, may be mentioned.

The fats can consist of an oil or wax or mixtures thereof, fatty acids, fatty acid esters, fatty alcohols, petroleum jelly, paraffin, lanolin, hydrogenated lanolin and acetylated lanolin. The oils may be chosen from animal, vegetable, mineral or ~a 17 synthetic oils, and in particular hydrogenated palm oil, hydrogenated castor oil, liquid petrolatum, paraffin oil, Purcellin oil, volatile or non-volatile silicone oils and isoparaffins.

When the cosmetic composition according to the invention is intended more especially for protecting the human epidermis against UV rays or as an antisun composition, it can take the form of a suspension or dispersion in solvents or fats, or alternatively the form of an emulsion (in particular of the O/W or W/O type, but preferably O/W) such as a cream or milk, or of a vesicular dispersion, or the form of an ointment, gel, solid stick or aerosol mousse. The emulsions can contain, in addition, anionic, nonionic, cationic or amphoteric surfactants.

When the composition according to the invention is used for protecting the hair, it can take the form of a shampoo, lotion, gel or composition to be rinsed, to be applied before or after shampooing, before or after dyeing or bleaching, before, during or after permanent-waving or straightening, styling or treatment lotion or gel, blow-drying or setting lotion or gel, hair lacquer or composition for permanentwaving or straightening, dyeing or bleaching the hair.

25 When the cosmetic composition according to the invention is used as a make-up product for the eyelashes, eyebrows, skin or hair, such as a cream for treating the epidermis, make-up foundation, lipstick,

~I

18 eyeshadow, blusher, eyeliner, mascara or colouring gel, it can be in solid or pasty, anhydrocs or aqueous form, such as oil-in-water or water-in-oil emulsions, suspensions or alternatively gels.

The subject of the invention is also a process for protecting the skin and hair against ultraviolet radiation, especially solar radiation, which consists in applying to the skin or hair an effective amount of the cosmetic composition defined above, or of a compound of formula or or alternatively of a benzotriazole derivative of formula as are defined above.

The examples which follow illustrate the invention without, however, limiting its scope.

EXAMPLE 1 This example illustrates the preparation of a compound according to the invention of formula: CH3 CH 3

CH

3 CH3.- Si- O i- O--Si CH3 I I A CH 3

CH

3 4 in which A represents: ;N OH c* N O-CH2-CH-CH 2 CH3 19 (this product corresponds to a compound of formula (1) for which R B CH,; r 0; s 1; Y OCH at position n 1; m 1 and X 0; p 1; Z CH,).

a) First stace: preparation of 4-(4-methoxy-2nitrophenylazo)benzene-1,3-diol A solution of diazonium salt, obtained beforehand by diazotization of 67.2 g (equivalent to 0.4 mol) of 4-methoxy-2-nitroaniline contained in 150 ml of concentrated HC1 with a sodium nitrite solution containing 28 g (equivalent to 0.4 mol) in 100 ml of water at 0-5 0 C, is added at a temperature of between 5 and 10°C and over one hour into a reactor containing 44 g (equivalent to 0.4 mol) of resorcinol dissolved in a mixture of 400 ml of ethanol and 400 ml of water. The mixture is left stirring for 2 hours. The red precipitate is filtered off and then rinsed copiously with water. 86 g (yield: 74 of the desired product are thereby obtained.

b) Second stacre: preparation of 2-(4-methoxy-2- 0 nitrophenylazo)-5-(2-methylallyloxy)phenol 81 g (equivalent to 0.28 mol) of the product Sobtained above, 220 ml of DMF and 42.6 g (equivalent to 0.308 mol) of potassium carbonate are introduced into a round-bottomed flask equipped with appropriate S 25 attachments. The mixture is brought to 80-90 0 C, and 28 g (equivalent to 0.308 mol) of methallyl chloride are then introduced into it dropwise over 30 minutes.

The mixture is then left stirring at 90 0 C for JL L s 4 h 30 min. The reaction mixture is then poured into 200 g of ice-cold water and the precipitate bbtained is filtered off. This precipitate is then taken up in dichloromethane, dried over sodium sulphate, concentrated and passed through a bed of silica After evaporation of the solvent and drying, 47 g of a red powder (yield: 49 consisting of the desired product are obtained.

c) Third stage: preparation of 2-(5-methoxy-2benzotriazolyl)-5-(2-methylallyloxy)phenol 32.54 g (equivalent to 0.134 mol) of the product obtained above and 400 ml of ethanol are placed in a round-bottomed flask. 48.4 g (equivalent to 0.269 mol) of glucose dissolved in 400 ml of 2N sodium hydroxide i added portionwise to it over half an hour, and the mixture is left stirring overnight.

44.4 g of powdered zinc are then added and the mixture is left stirring for 3 hours. The mixture is then S**filtered and the residue is washed with dichloromethane. The filtrate is extracted with dichloromethane. The organic liquors are combined, washed with water and dried. After concentration and drying, 36.6 g of a grey-brown-coloured powder are obtained. It is recrystallized in ethanol, thereby to obtain 41.8 g (yield: 65 of the desired product of formula: a~

CH

3

O

O-CH2-C=CH 2 CH3 d) Fourth stage: preparation of the desired final product A reactor equipped with all appropriate attachments is charged with 21.8 g of the product obtained above and 35 ml of toluene. The mixture is brought to 80°C under nitrogen. The catalyst (complex containing 3-3.5 by weight of Pt in cyclovinylmethylsiloxane from Hils Petrarch PC08E: 100 il) is added, and 16.5 g of heptamethyltrisiloxane are then added dropwise over 5 minutes. The heterogeneous mixture is brought to reflux for 8 hours under nitrogen. The reaction medium is concentrated and chromatography is then performed on silica under pressure (eluent: heptane with a gradient of CH 2 C1 2 25 g of a solid are then recovered, which is recrystallized in methanol to obtain finally 23.5 g (yield: 6- of the desired final product.

The UV absorption characteristics (measured in ethanol) of this product are as follows: 20 349 nm e 27,200 *5 Hence this product may be used very effectively as a sunscreen agent which is active in the

UV-A.

EXAMPLE 2 Following the same procedure as th-e one given in Example 1 (the only difference being that, in stage 1, 4-methoxy-2-nitroaniline has been replaced here by 2-nitroaniline), 8.5 g (yield: 67 were prepared of another compound according to the invention and corresponding to the following formula: CH3 CH 3

CH

3 I I I

CH

3 Si O i CH3 I I I A

C

3

CH

3 in which A in this instance represents: 7N

OH

o oo

I

CCC

O-C

H2

-CH-CH

2

I

CH

3 Hence this product differs from the one of 10 Example 1 above only in the absence of the OCH 3 substituent on the benzotriazole unit.

The UV absorption characteristics (measured in ethanol)of this product are as follows: 342 nm 24,500 15 Hence this product may be used very effectively as a sunscreen agent which is active in

TIV-A.

I

23 Tt will be noted that the intermediate product obtained at the end of stage No. 3 in the sequence of the process was of the formula: N OH

I

N

O-CH

2

-C=CH

2 CH3 EXAMPLE 3 Following the same procedure as the one given in Example 1 (the only difference being that, in stage 1, resorcinol was replaced here by 4-methyl-2- 2methylallyloxy)phenol), 2 g were prepared (yiAld, 54 of another compound according to the invention and corresponding to the following formula: N OH CH*. CH 3

CH

3

H

o. A CH 3 CH 3 6e in which A in this instance represents: a N'S .1 OH N N CH 2

-CHH

2 ao 3H3 Y N 6 e I e~ _rs--LB1 24 The UV absorption characteristics (measured in ethanol) of this product are as follows: 303 rnm e 10,900 348 nm e 22,200 Hence this product may be used very effectively as a sunscreen agent which is moderately active in the UV-B and strongly active in the UV-A.

It will be noeed that the intermediate product obtained at the end of stage No. 3 in the sequence of the process was of the formula: N OH C I OIN CH2-C=CH2 CH 30 N CH3

CH

3 EXAMPLE 4 Following the same procedure as the one given in Example 1 (the only differences being that, on the one hand, in stage 1, 4-methoxy-2-nitroailine and 15 resorcinol were replaced here by 2-nitroaniline and eugenol, respectively, and that, on the other hand, stage No. 2 was eliminated), 13 g (yield: 67 were prepared of another compound according to the invention S* t* and corresponding to the following formula: o Mw w

CH

3

CH

3

CH

3 I I-I CH3.-- Si- O CH 3 1 1 I A CH 3

CH

3 in which A in this instance represents: N OH

I

(CrNOCH 3

CH

2

CH

2

CH

2 The UV absorption characteristics (measured in ethanol) of this product are as follows: XA: 310 nm 17,800 Hence this product may be used very effectively as a sunscreen agent which is active in the e ao

UV-B.

It will be noted that the intermediate product obtained before carrying out the last step in 10 the sequence of the process was of the formula: N OH ON OCH3 2

CC

2 CH2CH=CH2 EXAMPLE A specific formulation of an antisun cosmetic composition according to the invention, namely an antisun cream, is illustrated here.

Compound of Example 1 5 g Mixture of cetyl/stearyl alcohol 7 g and oxyethylenated cetyl/stearyl alcohol containing 33 mol of EO ("SINNOVAX AO" from HENKEL) Non-self-emulsifying mixture of 2 g glycerol mono- and distearates Cetyl alcohol 1.5 g Benzoate of C 12

-C

15 alcohols 20 g ("FINSOLV TN" front WITCO) Polydimethyisiloxane 1.5 g Glycerol 17.5 g Perfume, preservative qs Water qs 100 g This cream is prepared according to the S: 20 traditional techniques for preparing emulsions, by dissolving the screening agent in the fatty phase ccntaining the emulsifiers, heating this fatty phase to about 70-80 0 C and adding the water, heated to the same temperature, with brisk stirring. The stirring is maintained for 10 to 15 minutes, the mixture is then allowed to cool with moderate stirring and, at about 0 C, perfume and preservative are finally added.

i I

Claims

1. Compounds of formulae: R R R R I I I I Sii I o- -L O 4r-0- R R A R r s R I si- 0 I R I Si- t oo oeoo o o go a e e A-Si(R') 3 (3) 5 in which formulae to R, which may be identical or different, are chosen from Ci-C 0 l alkyl, phenyl and 3,3,3-trifluoro- propyl radicals, at least 80 in numerical terms of the radicals R being methyl, B, which may be identical or different, are chosen from the above radicals R and the radical A defined below, which may be identical or different, are chosen from CI-C, alkyl radicals and phenyl 28 radicals, r is an integer between 0 and 50- inclusive, and s is an integer between 0 and 20 inclusive, on condition that, if s is zero, then at least one of the two symbols B denotes A, u is an integer between 1 and 6 inclusive, and t is an integer between 0 and 10 inclusive, on the understanding that t u is equal to or greater than 3, and the symbol A denotes a univalent radical linked directly to a silicon atom, and which corresponds to the following formula 6000 N (Y (4) e e (X)M-(CH 2 -CH-CH 2 in which formula Y, which may be identical or different, are go chosen from C 1 -C 8 alkyl radicals, halogens and C 1 -C 4 alkoxy radicals, on the understanding that, in the .0 latter case, two adjacent radicals Y on the same aromatic ring can form together an alkylidenedioxy group in which the alkylidene group contains from 1 to 2 carbon atoms, X represents O or NH, Z represents hydrogen or a CI-C 4 alkyl radical. 29 n is an integer between 0 and 3 inclusive, m is 0 or 1, on the understanding that, when m is zero, or when m is equal to 1 and X represents NH, then necessarily n cannot be zero and (ii) at least one of the radicals Y is an alkoxy radical, p represents an integer between 1 and inclusive.

2. Compounds according to Claim 1, corresponding to the formula or to the formula characterized in that the radicals R are alkyl radicals.

3. Compounds according to Claim 2, e: characterized in that the radicals R are methyl, ethyl, 15 propyl, n-butyl, n-octyl or 2-ethylhexyl radicals.

4, Compounds according to Claim 3, characterized in that the radicals R are methyl radicals.

5. Compounds according to any one of 20 the preceding claims, corresponding to the formula characterized in that the radicals B are alkyl radicals.

6. Compounds according to Claim characterized in that the radicals B are methyl, ethyl, propyl, n-butyl, n-octyl or 2-ethylhexyl radicals.

7. Compounds according to Claim 6, characterized in that the radicals B are methyl radicals. -I l~a~rm~cuP~

8. Compounds according to any one of the preceding claims, corresponding to the fbrmula characterized in that r is between 0 and 3 inclusive and s is between 0 and 3 inclusive.

9. Compounds according to any one of Claims 1 to 4, corresponding to the formula characterized in that t u is between 3 and inclusive.

Compounds according to Claim 1, corresponding to the formula characterized in that the radicals R' are alkyl radicals chosen from methyl, ethyl, propyl, n-butyl, n-octyl and 2-ethylhexyl radicals.

11. Compounds according to Claim 15 characterized in that the radicals R' are methyl e* radicals.

12. Compounds according to any one of the preceding claims, characterized in that n is not zero and preferably equal to 1 or 2, and Y is chosen 20 from methyl, tert-butyl and C 1 alkoxy.

13. Compounds according to Claim 12, characterized in that Y is methyl or methoxy.

14. Compounds according to Claim 13, characterized in that Y is methoxy.

15. Compounds according to any one of the preceding claims, characterized in that Z is hydrogen or methyl. AL/

16. Compounds according to any one of 1 ~1 Ilirc----l-~ 31 the preceding claims, characterized in that m is not zero and in that X represents 0.

17. Compounds according to any one of the. preceding claims, characterized in that p is equal to 1.

18. Compounds according to any one of the preceding claims, characterized in that the coupling of the chain link -(CH 2 )p-CH(Z)-CH 2 to the benzotriazole unit takes place at position 3, 4, 4' or 5 of the latter.

19. Compounds according to Claim 18, characterized in that the said coupling takes place at position 3, 4 or

20. Compounds according to any one of the preceding claims, characterized in that the coupling of the substituent Y to the benzotriazole unit takes place at position(s) 3, 4, 5 and/or 6 of the latter. 20

21. Use of the compounds of formulae or of the derivatives of formula (4a) as are defined in any one of Claims 1 to 20, as sunscreen agents which are active in the UV-A and/or UV-B range. 25

22. Cosmetic composition, especially for screening out ultraviolet rays, characterized in that it comprises, in a cosmetically acceptable vehicle, an effective amount of at least one of the compounds defined in any one of Claims 1 to S*

23. Cosmetic composition according to Claim 22, characterized in that the said cosmetically acceptable vehicle contains at least one fatty phase or one organic solvent.

24. Cosmetic composition according to Claim 23, fcharacterized in that the said vehicle takes the fotm of an \\MEtBOi\home$\Prlyanka\Keep\spec1\31700.95 cainws.doa 31/07/97 P -P U~ 32 oil-in-water or water-in-oil type emulsion, preferably oil- in-water.

Cosmetic composition according to one of Claims 22 to 24, characterized in that the content of screening compound(s) is between 0.1 and 20% by weight relative to the total weight of the composition.

26. Cosmetic composition according to Claim chara'cerized in that the said content is between 0.5 and by weight.

27. Process for protecting the skin and/or hair against ultraviolet radiation, especially solar radiation, characterized in that it consists in applying to the skin anu.'or hair an effective amount of at least one compound or of at least one derivative or of at least one composition as are defined in any one of the preceding claims. a 20 Dated this 31st day of July 1997 L' OREAL By their Patent Attorneys GRIFFITH HACK Fellows Institute of Patent 25 Attorneys of Australia o \\MEZ.BO1\home$\Priyanka\Keep\speci\3170 .95 claims.doc 31/07/97 i C 9 rY~ I I ABSTRACT NEW SUNSCREEN AGENTS, PHOTOPROTECTIVE COSMETIC COMPOSITIONS CONTAINING THEM AND USES The invention relates to new compounds of the short-chain, linear or cyclic diorganosiloxane type or of the triorganosi-ane type, possessing the common feature of all having at least one alkoxybenzotriazole function, these compounds being usable more especially as organic sunscreen agents in cosmetic compositions intended for protecting the skin and hair against ultraviolet radiation. The invention also relates to the use of the said compounds in the abovementioned cosmetic application, as well as to cosmetic compositions having improved properties containing them. Lastly, it also relates, as new industrial products which are useful per se, in particular as screening agents for photoprotective cosmetic U compositions for the skin and hair, to ethylenically a. unsaturated alkoxybenzotriazoles which are usable in s* the synthesis of the new compounds mentioned above. e OS.. IlrP'---M